CN103785354B - A kind of high-ratio surface Si carbon-base material for methane adsorption and preparation method thereof - Google Patents
A kind of high-ratio surface Si carbon-base material for methane adsorption and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of the Si carbon-base material for methane adsorption, comprise the steps: that (1) preparation mol ratio is Sodium Polyacrylate and the softex kw alkaline mixed solution of 0.006 ~ 0.05, add ethyl orthosilicate, react 3 ~ 5 hours at 30 ~ 50 DEG C; (2) take vinylidene chloride as monomer, azo-bis-iso-dimethyl is initator, joins in step (1) reacted solution, stir and add dispersant bentonite at 40 ~ 45 DEG C, reacts and obtains granulated polymer precursor in 10 ~ 15 hours; (3) the granulated polymer precursor that step (2) is obtained, after filtration, washing, can obtain for methane adsorption Si carbon-base material after dry, carbonization.The cost of material is low for the Si carbon-base prepared of the method, and have suitable specific area and pore volume, adsorbed methane performance is strong.
Description
Technical field
The present invention relates to a kind of high-ratio surface Si carbon-base material for methane adsorption and preparation method thereof.
Background technology
Along with rapid development of economy, energy supply and demand contradiction highlights, and the environmental pollution that the fossil energy such as coal, oil causes is day by day serious.Exploitation alternative energy source and the emphasis becoming and pay close attention to various countries of readjusting the energy structure.Gas reserves enriches, widely distributed, has the feature such as low stain, low cost.In recent years, the new technology that development of natural gas utilizes, especially replaces gasoline to become the focus of current research as clean motor vehicle fuel using natural gas.Compared with general liquid fuel, the energy density of natural gas is little, and calorific value is lower, so the efficient storage of natural gas is its key factor applied as motor vehicle fuel of restriction.At present, the method for natural gas-storing mainly contains three kinds, namely liquefies, compresses and adsorbs.Because the critical pressure of natural gas is high, critical-temperature is low, natural gas need be cooled to 111K just can make it liquefaction, so the energy that liquifying method consumes is more, natural gas applications cost significantly be increased.Compression method is that natural pressure is reduced to about 20MPa, makes it to become compressed natural gas, is stored in high-pressure cylinder.But compressed natural gas needs to set up special high pressure gas filling station, and cost of investment is high, higher-pressure storage containers is comparatively strict to the requirement of material simultaneously, and potential potential safety hazard is more.
For overcoming the shortcoming of compressed natural gas, various countries have extensively carried out the research of Adsorption Natural Gas technology.Adsorption Natural Gas technology is the adsorbent adopting high-ratio surface, is under low pressure realized the high density storage of natural gas by the suction-operated of micropore, reaches the storage capacity close with compressed natural gas.Compared with compressed natural gas, Adsorption Natural Gas technology has storage tank from heavy and light, the advantage such as security is good, operating cost is low, has significant economic advantages.Main component due to natural gas is methane, therefore designs and the efficient storage material of preparing adsorbed methane is the research emphasis of Adsorption Natural Gas technology.
Domestic and international many scholars are own to various sorbing material, as zeolite, molecular sieve, silica gel, carbon-based material etc. have carried out research and the evaluation of absorption property.Result shows, in carbon-based material, particularly active carbon, has abundant specific area, suitable pore-size distribution, huge micro pore volume, so the capacity of the charcoal absorption methane of unit volume is maximum.Current business-like normal activated carbon specific area is about 1200m
2/ g, because pore size distribution is too wide, under 298K, 3.4MPa, absorbing and storing methane content compresses the 1/2(QuinnDF storing methane content, MacdonaldJA.Carbon, 1992,30 (7): 1097 under being only equivalent to 20MPa).CN200610011229.0 discloses a kind of high molecular derivatives Si-C composite material for absorbing and storing methane and preparation method thereof.The method, in alkaline distilled water, adds surfactant and organo-silicon compound, is hydrolyzed and emulsification, then obtains polymer-silicon hybridization precursor by vinylidene chloride polymerisation.After the washing of this precursor, drying, under an inert atmosphere by its progressively carbonization, obtain required adsorbed methane composite.The composite obtained by the method has reasonable mechanical strength, and its specific area can reach 1700m
2/ more than g, pore volume can reach more than 0.90mL/g, at 25 DEG C, under the condition of 3.5MPa, can reach more than 140V/V to the adsorbance of methane, and adsorption activity needs to improve further.The block Carbon fibe prepared with NACF in US6475411 is 150V/V in 3.5MPa lower volume adsorbance, but is that raw material causes cost higher with Carbon fibe.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of high-ratio surface Si carbon-base material for methane adsorption and preparation method thereof.The cost of material is low for the Si carbon-base prepared of the method, and have suitable specific area and pore volume, adsorbed methane performance is strong.
For a preparation method for the high-ratio surface Si carbon-base material of methane adsorption, comprise the steps:
(1) prepare Sodium Polyacrylate and the softex kw alkaline mixed solution that mol ratio is 0.006 ~ 0.05, add ethyl orthosilicate, react 3 ~ 5 hours at 30 ~ 50 DEG C;
(2) take vinylidene chloride as monomer, azo-bis-iso-dimethyl is initator, joins in step (1) reacted solution, stir and add dispersant bentonite at 40 ~ 45 DEG C, reacts and obtains granulated polymer precursor in 10 ~ 15 hours;
(3) the granulated polymer precursor that step (2) is obtained, after filtration, washing, can obtain for methane adsorption high-ratio surface Si carbon-base material after dry, carbonization.
Alkaline mixed solution described in the inventive method step (1) adopts the mode adding inorganic base such as to add NaOH adjustment mixed solution pH to 10 ~ 12.Described Sodium Polyacrylate and the mol ratio of softex kw are 0.01 ~ 0.03.The described ethyl orthosilicate added and the mol ratio of softex kw are 0.05 ~ 0.45, are preferably 0.15 ~ 0.3.
The mol ratio of the rapid initator azo-bis-iso-dimethyl described in (2) of the inventive method and vinylidene chloride monomer is 0.005 ~ 0.04, is preferably 0.02 ~ 0.03.The ethyl orthosilicate added in step (1) and the mol ratio of vinylidene chloride are 0.02 ~ 0.5, are preferably 0.1 ~ 0.25.The mol ratio of the ethyl orthosilicate that step (1) adds and bentonite is 1.5 ~ 2.5.
Carbonisation described in the inventive method step (3) is preliminary carbonization 10 ~ 12h at 160 ~ 180 DEG C first, then carbonization 6 ~ 8 hours at 300 ~ 600 DEG C, finally carbonization 2 ~ 4 hours at 800 ~ 1000 DEG C.
For a high-ratio surface Si carbon-base material for methane adsorption, adopt above method to prepare, the specific area of this Si carbon-base material is 2300 ~ 2550m
2/ g, pore volume is 1.1 ~ 1.6cm
3/ g, average pore size 1.8 ~ 2.0nm.
Compared with prior art, a kind of high-ratio surface Si carbon-base material for methane adsorption of the present invention and preparation method thereof tool has the following advantages:
(1) the present invention adopts the softex kw mixture of doping Sodium Polyacrylate to be surfactant, specific area and the pore volume of Si carbon-base material can be increased substantially, make it have suitable aperture and uniform pore size distribution, under low pressure, improve the effect of methane adsorption;
(2) the inventive method is in polymerization process, take azo-bis-iso-dimethyl as initator, azo-bis-iso-dimethyl is a kind of oil-soluble azo-initiator, not cyano-containing, catabolite is nontoxic, and initiating activity is moderate, decomposes steadily, polymerisation easily controls, and occurs without residue and caking phenomenon;
(3) the inventive method preparation process is simple, and cost is low, is easy to methane adsorption and parsing, is suitable for commercial Application.
Detailed description of the invention
Further illustrate the high-ratio surface Si carbon-base material of the present invention for methane adsorption below by embodiment, but invention should not be deemed limited in following example.
embodiment 1
Take 0.11g Sodium Polyacrylate, 1.58g softex kw, 0.91g NaOH is dissolved in 100mL water, pH value of solution is 10 ~ 12, adds 7.5g ethyl orthosilicate, reacts 4 hours at 35 DEG C.Then 0.81g azo-bis-iso-dimethyl, 12.49g vinylidene chloride are added in reacted solution, stir and add 5.2g bentonite after 20 minutes, react and obtain granulated polymer precursor after 10 hours.After filtration, after washing, drying, first preliminary carbonization 10 ~ 12h at 160 ~ 180 DEG C, then carbonization 6 ~ 8 hours at 500 ~ 600 DEG C, finally carbonization 2 ~ 4 hours at 800 ~ 1000 DEG C, can obtain the high-ratio surface Si carbon-base material for methane adsorption, specific area is 2370m
2/ g, pore volume is 1.12cm
3/ g, average pore size 1.89nm.At 25 DEG C, under the condition of 3.0MPa, methane adsorption amount is 157V/V.
embodiment 2
Take 0.23g Sodium Polyacrylate, 2.23g softex kw, 0.91g NaOH is dissolved in 100mL water, pH value of solution is 10 ~ 12, adds 7.5g ethyl orthosilicate, reacts 4 hours at 40 DEG C.Then 0.87g azo-bis-iso-dimethyl, 15.21g vinylidene chloride are added in reacted solution, stir and add 5.6g bentonite after 20 minutes, react and obtain granulated polymer precursor after 10 hours.After filtration, after washing, drying, first preliminary carbonization 10 ~ 12h at 160 ~ 180 DEG C, then carbonization 6 ~ 8 hours at 500 ~ 600 DEG C, finally carbonization 2 ~ 4 hours at 800 ~ 1000 DEG C, can obtain the high-ratio surface Si carbon-base material for methane adsorption, specific area is 2430m
2/ g, pore volume is 1.18cm
3/ g, average pore size 1.94nm.At 25 DEG C, under the condition of 3.0MPa, methane adsorption amount is 145V/V.
embodiment 3
Take 0.41g Sodium Polyacrylate, 3.02g softex kw, 0.91g NaOH is dissolved in 100mL water, pH value of solution is 10 ~ 12, adds 7.5g ethyl orthosilicate, reacts 4 hours at 45 DEG C.Then 0.83g azo-bis-iso-dimethyl, 20.58g vinylidene chloride are added in reacted solution, stir and add 6.2g bentonite after 20 minutes, react and obtain granulated polymer precursor after 10 hours.After filtration, after washing, drying, first preliminary carbonization 10 ~ 12h at 160 ~ 180 DEG C, then carbonization 6 ~ 8 hours at 500 ~ 600 DEG C, finally carbonization 2 ~ 4 hours at 800 ~ 1000 DEG C, can obtain the high-ratio surface Si carbon-base material for methane adsorption, specific area is 2486m
2/ g, pore volume is 1.43cm
3/ g, average pore size 1.98nm.At 25 DEG C, under the condition of 3.0MPa, methane adsorption amount is 151V/V.
embodiment 4
Take 0.59g Sodium Polyacrylate, 3.68g softex kw, 0.91g NaOH is dissolved in 100mL water, pH value of solution is 10 ~ 12, adds 7.5g ethyl orthosilicate, reacts 4 hours at 45 DEG C.Then 0.91g azo-bis-iso-dimethyl, 29.15g vinylidene chloride are added in reacted solution, stir and add 6.8g bentonite after 20 minutes, react and obtain granulated polymer precursor after 10 hours.After filtration, after washing, drying, first preliminary carbonization 10 ~ 12h at 160 ~ 180 DEG C, then carbonization 6 ~ 8 hours at 500 ~ 600 DEG C, finally carbonization 2 ~ 4 hours at 800 ~ 1000 DEG C, can obtain the high-ratio surface Si carbon-base material for methane adsorption, specific area is 2503m
2/ g, pore volume is 1.51cm
3/ g, average pore size 2nm.At 25 DEG C, under the condition of 3.0MPa, methane adsorption amount is 155V/V.
comparative example 1
For the preparation method of the high-ratio surface Si carbon-base material of methane adsorption with embodiment 1, difference is, surfactant is softex kw, and initator is ABVN.The specific area of the high-ratio surface Si carbon-base material of preparation is 1940m
2/ g, pore volume is 0.93cm
3/ g, average pore size 1.92nm.At 25 DEG C, under the condition of 3.0MPa, methane adsorption amount is 125V/V.
Claims (10)
1. the preparation method for the Si carbon-base material of methane adsorption, it is characterized in that: comprise the steps: that (1) preparation mol ratio is Sodium Polyacrylate and the softex kw alkaline mixed solution of 0.006 ~ 0.05, add ethyl orthosilicate, react 3 ~ 5 hours at 30 ~ 50 DEG C; (2) take vinylidene chloride as monomer, azo-bis-iso-dimethyl is initator, joins in step (1) reacted solution, stir and add dispersant bentonite at 40 ~ 45 DEG C, reacts and obtains granulated polymer precursor in 10 ~ 15 hours; (3) the granulated polymer precursor that step (2) is obtained, after filtration, washing, can obtain for methane adsorption high-ratio surface Si carbon-base material after dry, carbonization.
2. method according to claim 1, is characterized in that: it is 10-12 that the alkaline mixed solution described in step (1) adopts the mode adding inorganic base to adjust mixed solution pH.
3. method according to claim 1, is characterized in that: described Sodium Polyacrylate and the mol ratio of softex kw are 0.01 ~ 0.03.
4. method according to claim 1, is characterized in that: the described ethyl orthosilicate added and the mol ratio of softex kw are 0.05 ~ 0.45.
5. method according to claim 4, is characterized in that: the described ethyl orthosilicate added and the mol ratio of softex kw are 0.15 ~ 0.3.
6. method according to claim 1, it is characterized in that: the mol ratio of the initator azo-bis-iso-dimethyl described in step (2) and vinylidene chloride monomer is 0.005 ~ 0.04, the ethyl orthosilicate added in step (1) and the mol ratio of vinylidene chloride are 0.02 ~ 0.5.
7. method according to claim 6, it is characterized in that: the mol ratio of the initator azo-bis-iso-dimethyl described in step (2) and vinylidene chloride monomer is 0.02 ~ 0.03, the ethyl orthosilicate added in step (1) and the mol ratio of vinylidene chloride are 0.1 ~ 0.25.
8. method according to claim 1, is characterized in that: the mol ratio of the ethyl orthosilicate that step (1) adds and bentonite is 1.5 ~ 2.5.
9. method according to claim 1, is characterized in that: carbonisation described in step (3) is preliminary carbonization 10 ~ 12h at 160 ~ 180 DEG C first, then carbonization 6 ~ 8 hours at 300 ~ 600 DEG C, finally carbonization 2 ~ 4 hours at 800 ~ 1000 DEG C.
10. for a Si carbon-base material for methane adsorption, it is characterized in that: adopt arbitrary described method preparation in claim 1 to 9, the specific area of this Si carbon-base material is 2300 ~ 2550m
2/ g, pore volume is 1.1 ~ 1.6cm
3/ g, average pore size 1.8 ~ 2.0nm.
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| US6475411B1 (en) * | 1998-09-11 | 2002-11-05 | Ut-Battelle, Llc | Method of making improved gas storage carbon with enhanced thermal conductivity |
| CN1554477A (en) * | 2003-12-26 | 2004-12-15 | 中国科学院山西煤炭化学研究所 | Process for preparing formed active carbon for storing methane |
| US7167354B2 (en) * | 2002-02-12 | 2007-01-23 | Tda Research, Inc. | Mesoporous carbons and polymers from hydroxylated benzenes |
| CN101003015A (en) * | 2006-01-18 | 2007-07-25 | 中国科学院化学研究所 | High molecular derivatives composite material used for absorbing and storing methane, and its preparing method |
| CN101497020A (en) * | 2009-01-21 | 2009-08-05 | 哈尔滨工业大学 | Method for preparing mesoporous silicon adsorption material with high specific surface area |
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| US6475411B1 (en) * | 1998-09-11 | 2002-11-05 | Ut-Battelle, Llc | Method of making improved gas storage carbon with enhanced thermal conductivity |
| US7167354B2 (en) * | 2002-02-12 | 2007-01-23 | Tda Research, Inc. | Mesoporous carbons and polymers from hydroxylated benzenes |
| CN1554477A (en) * | 2003-12-26 | 2004-12-15 | 中国科学院山西煤炭化学研究所 | Process for preparing formed active carbon for storing methane |
| CN101003015A (en) * | 2006-01-18 | 2007-07-25 | 中国科学院化学研究所 | High molecular derivatives composite material used for absorbing and storing methane, and its preparing method |
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